CN106062025A

CN106062025A - Method for producing a thermoplastic copolymers from polycaprolactam and thermoplastic polyurethane

Info

Publication number: CN106062025A
Application number: CN201580011610.4A
Authority: CN
Inventors: P·德斯保斯; R·霍尔曼; D·肯普弗特; B·布鲁赫曼; F·蒂尔贝尔; R·穆勒豪普特
Original assignee: BASF SE
Current assignee: BASF SE
Priority date: 2014-01-31
Filing date: 2015-01-30
Publication date: 2016-10-26
Anticipated expiration: 2035-01-30
Also published as: WO2015114076A1; CN106062025B; US20160340465A1; EP3099724B1; EP3099724A1; US10329374B2

Abstract

The invention relates to a method for producing a thermoplastic copolymer from polycaprolactam and thermoplastic polyurethane (TPU), to thermoplastic copolymers obtained according to said method and to moulded bodies produced from said copolymers.

Description

The method being prepared thermoplastic copolymer by polycaprolactam and thermoplastic polyurethane

The present invention relates to a kind of by polycaprolactam and thermoplastic polyurethane (TPU) prepare thermoplastic copolymer method, Thus obtained thermoplastic copolymer and the moulded products formed by the copolymer of the type.

Two or more polymer can carry out combined polymerization to obtain tool compared with the original copolymer used with melt There are the chemistry of improvement and/or the copolymer of mechanical property.Even if being used as polymer unmixing or the only partial miscibility of raw material, two kinds Or the melt of more kinds of polymer is also copolymerizable, because the copolymer formed in copolymerization process is in unmixing or portion The effect of bulking agent is played, to reduce between unmixing or the polymer of partial miscibility at phase boundray between point miscible polymer Interfacial tension, and increase the adhesive force between unmixing or the polymer of partial miscibility.

Documents below discloses is prepared blend by polycaprolactam and thermoplastic polyester type polyurethane elastomer (TPEU) Method: G.S.Yang et al., " Preparation and characterisation of thermoplastic polyurethane elastomer and polyamide 6 blends by in situ anionic ring-opening Polymerization of ε-caprolactam ", Polymer Engineering and Science 2006,46, the 1196-1203 page, and G.S.Yang et al., " A novel approach to the preparation of thermoplastic polyurethane elastomer and polyamide 6 blends by in situ Anionic ring-opening polymerisation of epsilon-caprolactam ", Polym.Int.2006, 55, the 643-649 page.These blends are by being mixed into acyl in oneself using sodium caprolactam as polymerization catalyst at 160 DEG C Obtaining in amine and the mixture of TPEU, described TPEU is based on poly-(tetramethylene ether glycol) and methylenediphenyl diisocyanates (MDI).This mixture is kept at 160 DEG C 30min, and at 180 DEG C, is polymerized 60min.The side that G.S.Yang et al. describes Method disadvantageously, polymerization be to carry out at a higher temperature and last longer.The method another disadvantageously, Thus obtained blend needs heavy post processing to extract in THF；Being dissolved in formic acid, the THF by excess is anti- Precipitate again from described blend, separate copolymer based on TPEU and polycaprolactam.

DE 10 2,006 036 539 A1 discloses and is prepared can be added by thermoplastic by the mixture of polyamide and thermoplastic polyurethane The method of work moulding material.Described moulding material passes through at a temperature of in the range of 180 DEG C to 260 DEG C at base catalyst In the presence of make the melt comprising C4-C12 lactams or lactam mixture carry out in-situ polymerization with thermoplastic polyurethane and be formed. The copolymer of polyamide and thermoplastic polyurethane is formed in this polymerization process.In preferred embodiments, will at 100 DEG C Acetanilide sodium (sodium acetanilide) is mixed into following mixture as polymerization catalyst: acyl in single 12 Amine or with the lauric lactam of caprolactam combination with based on polycaprolactone and methylenediphenyl diisocyanates (MDI) The mixture of thermoplastic polyurethane, then carrys out induced polymerization by the temperature of mixture is increased to 225 DEG C-240 DEG C.DE 10 The method of 2006 036 539 A1 disadvantageously, described polymerization is carried out at a higher temperature.

It is an object of the present invention to provide a kind of improvement being prepared copolymer by polycaprolactam and thermoplastic polyurethane Method.

Unexpectedly, we have found that this purpose is prepared heat by a kind of by polycaprolactam and thermoplastic polyurethane The method of plastic copolymer realizes, and described method make use of specific thermoplastic polyurethane to allow use particularly advantageous, low Polymerization temperature.

Therefore, the present invention provides a kind of for preparing based on polycaprolactam and the thermoplastic copolymer of thermoplastic polyurethane Method, comprising:

A) caprolactam is provided；

B) providing thermoplastic polyurethane, it has melt temperature T₀And based on

(i) alkylene diisocyanate；

(ii) aklylene glycol；With

(iii) polyalkylene ether；

C) at T₁At a temperature of preparation comprise described caprolactam and the liquefied mixture of described thermoplastic polyurethane；

D) polymerization catalyst is mixed into the liquefied mixture in c) to obtain following mixture: described mixture comprises Described caprolactam is 3:1 to 1:4 with the mass ratio of described thermoplastic polyurethane and caprolactam and thermoplastic polyurethane, then Temperature T of up to 175 DEG C₂Under carry out being polymerized to obtain described thermoplastic copolymer.

Unexpectedly, we have found that step b) provides specific aliphatic thermoplastic polyurethane make according to d) Polymerization can be at particularly advantageous, low polymerization temperature T₂Carry out at up to 175 DEG C, without in polymerization mixing Thing causes destructive crystallization and/or precipitation.Compared with prior art, relatively low polymerization temperature T₂Also preventing can be higher poly- The disadvantageous side reaction occurred at a temperature of conjunction.Advantageously, this can cause by-product to reduce, thus increases the yield of described method also And the purification of beneficially end product.Unexpectedly, it has been found that, provide aliphatic thermoplastic polyurethane to make according to step b) Must according to d) carry out speed ratio caprolactam and the aromatics thermoplastic polyurethane being polymerized combined polymerization speed faster, described aromatics In thermoplastic polyurethane, at least one in diisocyanate, glycol and ether component comprises aromatic fractions.

It is a further object to provide polycaprolactam and the thermoplastic polyurethane of the mechanical property with improvement Copolymer.

Unexpectedly, we have found that this purpose is by selecting specific thermoplastic polyurethane being total to as the present invention The component of polymers and realize, the copolymer of the described present invention is based on polycaprolactam and thermoplastic polyurethane.By described specific Thermoplastic polyurethane favourable mechanical property can be given the copolymer of the present invention.

Therefore, the present invention also provides for a kind of based on polycaprolactam with the thermoplastic copolymer of thermoplastic polyurethane, described Thermoplastic polyurethane based on

(i) alkylene diisocyanate；

(ii) aklylene glycol；With

(iii) polyalkylene ether,

Wherein said copolymer comprises 25 weight % to the thermoplastic polyurethane of 80 weight % (percentage by weight), based on depositing The caprolactam being in copolymer and the summation meter of the weight of thermoplastic polyurethane.

A further object of the present invention is to be prepared by thermoplastic copolymer based on polycaprolactam and thermoplastic polyurethane The moulded products of the mechanical property with improvement.

Unexpectedly, we have found that this purpose is realized by the moulded products obtained by the copolymer of the present invention.

Therefore, the present invention also provides for that a kind of thermoplastic copolymer by the present invention obtains or can be by the thermoplasticity of the present invention The moulded products that copolymer obtains.

Step a)

In principle, the offer in step a) special is not limited by any.Such as, a) in caprolactam can be with solid State provides, such as, such as the form with powder or pellet.Or, described caprolactam can provide with molten condition, in these feelings Under condition, preferably it is being not less than 80 DEG C, more preferably 100 DEG C to 175 DEG C, more preferably 100 DEG C to 160 DEG C, more preferably 110 DEG C to 150 Caprolactam is made to melt at a temperature of DEG C.The caprolactam passing through a) to provide is preferably solid state or molten condition, more preferably For molten condition.

Step b)

I () alkylene diisocyanate, (ii) aklylene glycol are not subject to the alkylene moiety in (iii) polyalkylene ether Any special restriction, and can be the most each substituted or unsubstituted state.Such as, the alkylidene of state it is replaced Part preferably has one or more than one substituent group, more preferably one to three substituent group, more preferably one substituent group.Substituent group Can be similar and different.Such as, substituent group must be inertia under conditions of step c) or step d), here it is preferably alkyl portion The reason divided.C1-C6 moieties be it is furthermore preferred that and C1-C3 moieties even more preferably from.

I () alkylene diisocyanate, (ii) aklylene glycol are preferred with the alkylene moiety in (iii) polyalkylene ether For unsubstituted state.

I the alkylene diisocyanate in () is preferably selected from C1 to C20 alkylene diisocyanate and two or more The mixture planted, is more preferably selected from C3 to C18 alkylene diisocyanate and the mixture of two or more thereof, more preferably selects From C6 to C13 alkylene diisocyanate and the mixture of two or more thereof, being more preferably selected from 1,6-hexa-methylene two is different Cyanate (HDI), 4,4 '-diisocyanate base dicyclohexyl methyl hydride (H12MDI), 1-NCO-3-NCO first Base-3,5,5-trimethyl-cyclohexane (IPDI) and the mixture of two or more thereof.

Such as, C1 to C20 alkylene diisocyanate is selected from C1 alkylene diisocyanate, C2 alkylidene two Carbimide. Ester, C3 alkylene diisocyanate, C4 alkylene diisocyanate, C5 alkylene diisocyanate, C6 alkylidene two Carbimide. Ester, C7 alkylene diisocyanate, C8 alkylene diisocyanate, C9 alkylene diisocyanate, C10 alkylidene two Carbimide. Ester, C11 alkylene diisocyanate, C12 alkylene diisocyanate, C13 alkylene diisocyanate, C14 alkylidene two are different Cyanate, C15 alkylene diisocyanate, C16 alkylene diisocyanate, C17 alkylene diisocyanate, C18 alkylidene Diisocyanate, C19 alkylene diisocyanate, C20 alkylene diisocyanate and the mixture of two or more thereof, and C6 to C13 alkylene diisocyanate is different selected from C6 alkylene diisocyanate, C7 alkylene diisocyanate, C8 alkylidene two Cyanate, C9 alkylene diisocyanate, C10 alkylene diisocyanate, C11 alkylene diisocyanate, C12 alkylidene two Isocyanates, C13 alkylene diisocyanate and the mixture of two or more thereof.

(ii) aklylene glycol in is preferably selected from C1 to C20 aklylene glycol and the mixture of two or more thereof, It is more preferably selected from C3 to C8 aklylene glycol and the mixture of two or more thereof, is more preferably selected from C4 to C6 aklylene glycol And the mixture of two or more, be more preferably selected from BDO, 1,6-hexanediol and mixture thereof.

Such as, C1 to C20 aklylene glycol is selected from C1 aklylene glycol, C2 aklylene glycol, C3 aklylene glycol, C4 Asia Alkyl diol, C5 aklylene glycol, C6 aklylene glycol, C7 aklylene glycol, C8 aklylene glycol, C9 aklylene glycol, C10 Aklylene glycol, C11 aklylene glycol, C12 aklylene glycol, C13 aklylene glycol, C14 aklylene glycol, C15 alkylidene Glycol, C16 aklylene glycol, C17 aklylene glycol, C18 aklylene glycol, C19 aklylene glycol, C20 aklylene glycol and Its two or more mixture, and C3 to C8 aklylene glycol is selected from C3 aklylene glycol, C4 aklylene glycol, C5 alkylene Base glycol, C6 aklylene glycol, C7 aklylene glycol, C8 aklylene glycol and the mixture of two or more thereof.

(iii) polyalkylene ether in is preferably selected from poly-(C1 to C20 alkylidene) ether and the mixing of two or more thereof Thing, further preferably selected from poly-(C2 to C12 alkylidene) ether and the mixture of two or more thereof, further preferably selected from poly- (C2 to C6 alkylidene) ether and the mixture of two or more thereof, wherein the polyalkylene ether in (iii) is more preferably PolyTHF.

Such as, poly-(C1 to C20 alkylidene) ether is selected from poly-(C1 alkylidene) ether, poly-(C2 alkylidene) ether, poly-(C3 alkylene Base) ether, poly-(C4 alkylidene) ether, poly-(C5 alkylidene) ether, poly-(C6 alkylidene) ether, poly-(C7 alkylidene) ether, poly-(C8 alkylene Base) ether, poly-(C9 alkylidene) ether, poly-(C10 alkylidene) ether, poly-(C11 alkylidene) ether, poly-(C12 alkylidene) ether, poly-(C13 is sub- Alkyl) ether, poly-(C14 alkylidene) ether, poly-(C15 alkylidene) ether, poly-(C16 alkylidene) ether, poly-(C17 alkylidene) ether, poly- (C18 alkylidene) ether, poly-(C19 alkylidene) ether, poly-(C20 alkylidene) ether and the mixture of two or more thereof, and poly-(C2 To C6 alkylidene) ether selected from poly-(C2 alkylidene) ether, poly-(C3 alkylidene) ether, poly-(C4 alkylidene) ether, poly-(C5 alkylidene) ether, Poly-(C6 alkylidene) ether and the mixture of two or more thereof.

I alkylene moiety that () alkylene diisocyanate, (ii) aklylene glycol are concrete with in (iii) polyalkylene ether The carbon atom number specified refers to the total number of carbon atom in alkylene moiety.Such as, " C20 alkylidene " is understood to mean that tool There is the alkylene moiety of 20 carbon atoms.

(iii) number-average molecular weight (M of the polyalkylene ether in_n) it is preferably 300g to 8000g, more preferably 600g extremely 4500g, more preferably 800g to 2500g.

Preferably, b) in thermoplastic polyurethane based on following material: according to (i) selected from C1 to C20 alkylidene two isocyanide Acid esters and the alkylene diisocyanate of the mixture of two or more thereof；According to (ii) selected from C1 to C20 aklylene glycol And the aklylene glycol of the mixture of two or more；It is selected from poly-(C1 to C20 alkylidene) ether and two with according to (iii) Kind or the number-average molecular weight (M of more kinds of mixture_n) it is the polyalkylene ether of 300g to 8000g.It is highly preferred that the heat in b) Plastic polyurethane is based on following material: according to (i), selected from C6 to C13 alkylene diisocyanate and two or more is mixed The alkylene diisocyanate of compound；According to (ii) selected from C4 to C6 aklylene glycol and the mixture of two or more thereof Aklylene glycol；With the number-average molecular weight (M being selected from poly-(C2 to C6 alkylidene) ether according to (iii)_n) it is the poly-of 600g to 4500g Alkylene ether.It is highly preferred that the thermoplastic polyurethane in b) is based on following material: according to (i) selected from 1,6-hexa-methylene two is different Cyanate (HDI), 4,4 '-diisocyanate base-dicyclohexyl methyl hydride (H12MDI), 1-NCO-3-NCO Methyl-3,5,5-trimethyl-cyclohexane (IPDI) and the alkylene diisocyanate of the mixture of two or more thereof；According to (ii) it is selected from 1,4-butanediol and 1,6-HD or the aklylene glycol of its mixture；It is selected from the equal molecule of number with according to (iii) Amount (M_n) it is the polyalkylene ether of the PolyTHF of 800g to 2500g.It is highly preferred that thermoplastic polyurethane in b) based on Lower material: (i) 1,6-hexamethylene diisocyanate (HDI) or 4,4'-diisocyanate base dicyclohexyl methyl hydride (H12MDI)； (ii) 1,4-butanediol or 1,6-HD；(iii) number-average molecular weight (M_n) it is the PolyTHF of 800g to 2500g.

Preferably, in component alkylene diisocyanate (i), aklylene glycol (ii) and polyalkylene ether (iii) Kind or more kinds of, more preferably two or more, the most all there is straight chain and/or cyclic alkylidene part.It is highly preferred that Described alkylene diisocyanate (i) has straight chain and/or cyclic alkylidene part, and described aklylene glycol (ii) has straight chain Alkylene moiety and described polyalkylene ether (iii) have straight-chain alkyl-sub-part.

As used in this description, term " straight chain and/or cyclic alkylidene part " is understood to mean that by least one The alkylene moiety that individual straight-chain alkyl-sub-part and at least one cyclic alkylidene part are combined into, such as 4,4 '-two Carbimide .s The dicyclohexyl methyl hydride part of ester group dicyclohexyl methyl hydride (H12MDI).

Number-average molecular weight (the M of the thermoplastic polyurethane in b)_n) it is preferably 10000g to 300000g, more preferably 15000g to 200000g, more preferably 19000g to 160000g.

Melt temperature T of the thermoplastic polyurethane in b)₀Being preferably 155 DEG C to 280 DEG C, more preferably 160 DEG C to 250 DEG C, more preferably 170 DEG C to 230 DEG C.

Step c)

The term " liquefied mixture " used in c) is understood to mean that in temperature T₁Lower by thermoplastic polyurethane dissolving The mixture formed in molten caprolactam.When temperature T₁More than or equal to melt temperature T₀Time, at least some thermoplastic poly ammonia Ester can melt, and is therefore present in mixture with liquid condition, and is not necessarily dissolved by the caprolactam melted.

Prepare liquefied mixture according to step c) special not limited by any.Preferably, T₁It is not more than T₀.It is highly preferred that T₁It is 100 DEG C to 175 DEG C, more preferably 100 DEG C to 160 DEG C, more preferably 110 DEG C to 150 DEG C.Therefore, c) in mixture Can be at favourable low temperature T₁Lower offer, this not only reduces the energy that the method step needs, the most also before the polymerization in d) It is effectively prevented the formation of undesirable by-product.

Step d)

Unexpectedly, by means of the special chemical property of the aliphatic thermoplastic polyurethane in b), d) in polymerization can Polymerization temperature T in a wide range₂Under implement with the highest rate of polymerization.D) temperature T in₂It is preferably 100 DEG C to 175 DEG C, more preferably 115 DEG C to 170 DEG C, more preferably 130 DEG C to 170 DEG C.Also it may be preferred that T₂Not less than T₁, and temperature difference T₂-T₁ More preferably 0 DEG C to 40 DEG C, more preferably 0 DEG C to 30 DEG C, more preferably 0 DEG C to 20 DEG C.

Preferably, temperature T₂It is 100 DEG C to 175 DEG C and temperature difference T₂-T₁It it is 0 DEG C to 40 DEG C.It is highly preferred that temperature T₂It is 130 DEG C to 170 DEG C and temperature difference T₂-T₁It it is 0 DEG C to 20 DEG C.Or, it is preferable to, temperature T₂It it is 100 DEG C to 175 DEG C and T₁It it is 100 DEG C To 175 DEG C, it is highly preferred that temperature T₂It it is 130 DEG C to 170 DEG C and T₁It it is 110 DEG C to 150 DEG C.

Unexpectedly, we have found that, when the salt of use caprolactam is as polymerization catalyst, according to gathering d) Conjunction can be carried out with the highest rate of polymerization.Therefore, d) in polymerization catalyst be preferably the salt of caprolactam, more preferably For alkali metal salt or the alkali salt of caprolactam, the more preferably alkali metal salt of caprolactam, more preferably caprolactam The sodium salt of sodium salt or potassium salt, more preferably caprolactam.

Preferably, in d), the amount of the polymerization catalyst being mixed into is 0.2 weight % to 4 weight %, preferably 0.4 weight % To 3.4 weight %, more preferably 0.6 weight % to 3 weight %, based on caprolactam and the summation of the weight of thermoplastic polyurethane Meter.

Optionally, step d) is additionally mixed into polymerization activator.Described polymerization activator is preferably selected from N-carbonyl and replaces Lactams, aliphatic series and aromatic diisocyanates, allophanate, polyisocyanates, aliphatic series and aromatics diacyl halogen and two Kind or more kinds of mixture.It is highly preferred that described polymerization activator is selected from N, N '-C1-to N, N '-C20-alkylenediamino Formoxyl caprolactam, N-acetyl group C3-C10 lactams, C2-C16 alkylene diisocyanate, C5-C12 arlydene two isocyanide Acid esters or C5-C16 arylidene alkylene diisocyanate, C1-C6 alkylidene allophanate, the many isocyanides of C12-C24 alkylidene Acid esters, C2-C16 alkylidene diacyl halogen, C5-C12 arlydene diacyl halogen or C5-C16 arylidene alkylene diacyl halogen and Its two or more mixture.It is highly preferred that described polymerization activator is selected from N, N '-C3-to N, N '-C8-alkylidene two Carbamoyl caprolactam, N-acetyl group C4-C8 lactams, C4-C13 alkylene diisocyanate, C6-C10 arlydene two Isocyanates or C7-C10 arylidene alkylene diisocyanate, C2-C4 alkylidene allophanate, C16-C20 alkylidene are many Isocyanates, C4-C13 alkylidene diacyl halogen, C6-C10 arlydene diacyl halogen or C8-C12 arylidene alkylene diacyl Halogen and the mixture of two or more thereof.It is highly preferred that described polymerization activator is selected from N, N '-hexa-methylene-1,6-diamino Base formoxyl caprolactam, vinylcaprolactam, tetramethylene diisocyanate, hexamethylene diisocyanate, di-2-ethylhexylphosphine oxide (cyclohexyl isocyanate)；Toluene di-isocyanate(TDI), ethyl allophanate, the three of 1,6-hexamethylene diisocyanate (HDI) Aggressiveness, butylidene diacyl bromine, hexa-methylene diacyl chlorine, 4,4 '-di-2-ethylhexylphosphine oxide (cyclohexyl acid chloride), tolyl methylene Diacyl chlorine and the mixture of two or more thereof.

The iactame moiety of polymerization activator, alkylene moiety, arylene portion and arylidene alkylene part are specified Carbon atom number refer in concrete iactame moiety, alkylene moiety, arylene portion and arylidene alkylene part The total number of carbon atom.Such as, " C16 alkylidene " is interpreted as the alkylene moiety with 16 carbon atoms, simultaneously " in C10 Amide " it is interpreted as the iactame moiety with 10 carbon atoms.

Term " arylidene alkylene " is understood to mean that by least one arylene group and at least one alkylidene base The part that group is constituted.Described " arylidene alkylene " part special is not limited by any.Such as, C13 arylidene alkylene portion Point it is preferably selected from diphenyl methane, such as, 2,2 '-diphenyl methane, 2,4 '-diphenyl methane or 4,4 '-diphenyl methane.

Preferably, polymerization activator selected from N, N '-alkylenediamino formoxyl caprolactam and two or more Mixture.It is highly preferred that polymerization activator selected from N, N '-C1 to N, N '-C20 alkylenediamino formoxyl caprolactam and Its two or more mixture, is more preferably selected from N, N '-C2 to N, N '-C12 alkylenediamino formoxyl caprolactam And the mixture of two or more, it is more preferably selected from N, N '-C3 to N, N '-C8 alkylenediamino formoxyl caprolactam And the mixture of two or more.It is highly preferred that polymerization activator is N, N '-hexa-methylene-1,6-dicarbamoyl base Caprolactam.

In d), the amount of the polymerization activator being mixed into is preferably 0.5 weight % to 15 weight %, more preferably 1 weight % To 12 weight %, more preferably 2 weight % to 9 weight %, based on caprolactam and the summation meter of the weight of thermoplastic polyurethane.

Unexpectedly, we have found that by the mass ratio selecting caprolactam and thermoplastic polyurethane, can be to have Mechanical property is given according to thermoplastic copolymer d) obtained by the mode of profit.Preferably, according to d) polymerization catalyst being mixed into To the liquefied mixture in c), obtain following mixture: described mixture comprise caprolactam with in thermoplastic polyurethane and oneself Amide is 7:3 to 1:3 with the mass ratio of thermoplastic polyurethane, is preferably 2:1 to 3:7, is more preferably 16:9 to 9:16.

The content of the lactams according to copolymerization non-in thermoplastic copolymer d) obtained is preferably not greater than 10 weight %, more Preferably not greater than 7 weight %, more preferably not more than 5 weight %, lactams based on thermoplastic copolymer and non-copolymerization The summation meter of weight.

Preferably such a is prepared based on polycaprolactam and the method for the thermoplastic copolymer of thermoplastic polyurethane, Comprising:

A) caprolactam is provided；

B) providing thermoplastic polyurethane, it has melt temperature T of 160 DEG C to 250 DEG C₀And based on

(i) C3 to C18 alkylene diisocyanate；

(ii) C3 to C8 aklylene glycol；With

(iii) there is the number-average molecular weight (M of 600g to 4500g_n) poly-(C2 to C6 alkylidene) ether；

C) temperature T of 100 DEG C to 175 DEG C₁Lower preparation comprises described caprolactam and the liquid of described thermoplastic polyurethane State mixture；

D) by oneself of summation meter 0.4 weight % of weight based on caprolactam and thermoplastic polyurethane to 3.4 weight % The alkali metal salt of lactams or alkali salt are mixed into the liquefied mixture in c) as polymerization catalyst, following to obtain Mixture: described mixture comprises described caprolactam and described thermoplastic polyurethane and caprolactam and thermoplastic polyurethane Mass ratio is 3:1 to 1:4, then temperature T of 100 DEG C to 175 DEG C₂Under carry out being polymerized to obtain described thermoplastic copolymer.

A) caprolactam is provided；

(i) C3 to C18 alkylene diisocyanate；

(ii) C3 to C8 aklylene glycol；With

D) also include the polymerization activator being mixed into 1 weight % to 12 weight %, based on caprolactam and thermoplastic poly The summation meter of the weight of urethane, wherein said polymerization activator is selected from N, N '-C2 to N, N '-C12 alkylenediamino formoxyl Caprolactam and the mixture of two or more thereof.

In the method for the invention, according to preparation c) with according to being mixed into and being polymerized with discontinuous method or continuation method d) Carry out.

Batch mode of operation

The method of the present invention can be implemented with discontinuous method, c) in preparation and d) in be mixed into and be polymerized with interval side Method is carried out, and is wherein molten condition according to caprolactam a) provided and is solid, shaped according to thermoplastic polyurethane b) provided State, and c) in liquefied mixture by thermoplastic polyurethane mixing is provided in the caprolactam of molten condition.

Have a rest here in method, preferably by the mixture in c) in temperature T₁Lower holding 1min to 1.5h, more preferably 10min To 70min, more preferably 20min to 60min.

Unexpectedly, we have found that work as polymerization catalyst to comprise the liquid of polymerization catalyst and caprolactam When the form of mixture mixes, the polymerization that this discontinuous method is particularly used in implementing d) in a mold is to obtain moulded products. Therefore preferably the form of the polymerization catalyst liquefied mixture to comprise polymerization catalyst and caprolactam is mixed in step d) Enter.

Term " liquefied mixture comprising polymerization catalyst and caprolactam " is understood to mean that and is divided by polymerization catalyst Dissipate or be dissolved in the mixture formed in caprolactam melted, liquid.

Preferably, the liquefied mixture comprising polymerization catalyst and caprolactam described in is by being mixed by polyalcohol catalyst Enter and provide to the caprolactam of molten condition.

The amount of the polymerization catalyst that the liquefied mixture comprising polymerization catalyst and caprolactam preferably comprises is 2 weight % To 40 weight %, more preferably 4 weight % to 34 weight %, more preferably 6 weight % to 30 weight %, based on caprolactam Weight meter.

Preferably, the liquefied mixture of polymerization catalyst and caprolactam will be comprised in temperature T₃Lower holding 1min is extremely 1.5h, more preferably 10min to 70min, more preferably 20min to 60min.

Temperature T₃It is generally free from any restriction.T₃Be preferably 100 DEG C to 175 DEG C, more preferably 105 DEG C to 155 DEG C, more excellent Elect 110 DEG C to 130 DEG C as.

The most optionally being mixed into polymerization activator in d), be mixed into by the most described polymerization activator in c) is mixed In compound.Preferably, being mixed into the amount of the polymerization activator to the mixture in c) is 1 weight % to 30 weight %, more preferably It is 2 weight % to 24 weight %, more preferably 4 weight % to 18 weight %, based on caprolactam and the weight of thermoplastic polyurethane The summation meter of amount.

Preferably, in d), by the liquefied mixture comprising polymerization catalyst and caprolactam with c) in liquid mix Thing mixes, and comprise polymerization catalyst and the mixture of caprolactam and c) in the mass ratio of mixture be 1:4 to 3:1, more It is preferably 1:3 to 2:1, more preferably 1:1.5 to 1.5:1.Preferably in temperature T₄Lower will comprise polymerization catalyst and caprolactam Liquefied mixture with c) in liquefied mixture mix.Described temperature T₄It is preferably 100 DEG C to 175 DEG C, more preferably 105 DEG C extremely 155 DEG C, more preferably 110 DEG C are to 130 DEG C.

D) polymerization in preferably carries out 0.1min to 20min, more preferably 0.3min to 10min, more preferably 0.5min extremely 3min。

Preferably, in above-mentioned discontinuous method, d) in polymerization carry out in a mold, more preferably at reaction injection molding (RIM) mould is carried out.

A) caprolactam is provided；

(i) C3 to C18 alkylene diisocyanate；

(ii) C3 to C8 aklylene glycol；With

C) temperature T of 100 DEG C to 160 DEG C₁Lower preparation comprise described caprolactam and described thermoplastic polyurethane Liquefied mixture；

D) by oneself of summation meter 0.4 weight % of weight based on caprolactam and thermoplastic polyurethane to 3.4 weight % The alkali metal salt of lactams or alkali salt are mixed into the liquefied mixture in c) following to obtain as polymerization catalyst Mixture: described mixture comprises described caprolactam and described thermoplastic polyurethane, and caprolactam and thermoplastic polyurethane Mass ratio be 3:1 to 1:4, and temperature T of 115 DEG C to 170 DEG C₂Under carry out being polymerized to obtain described thermoplastic copolymer, Polymerization in d) carries out 0.3min to 10min,

Preparation in c) and d) in be mixed into and be polymerized be to carry out with discontinuous method, and wherein according to a) provide oneself Lactams is molten condition, and is solid state according to thermoplastic polyurethane b) provided, and c) in liquefied mixture be logical Crossing to be mixed into thermoplastic polyurethane provides to the caprolactam of molten condition.

Or, the method for the present invention with discontinuous method implement, c) in preparation and d) in be mixed into and be polymerized be with Discontinuous method is carried out, and is wherein solid state according to caprolactam a) provided, and according to thermoplastic polyurethane b) provided For solid state, and in c), caprolactam mix with thermoplastic polyurethane and will the mixture heating of acquisition by mediating To T₁.In this alternative intermittent mode, the mixture in preferably making c) is at T₁Lower holding 0.1min to 20min, more preferably 0.3min to 16min, more preferably 0.5min to 12min.

Particularly preferably such a prepares thermoplastic copolymer based on polycaprolactam and thermoplastic polyurethane Method, comprising:

A) caprolactam is provided；

(i) C3 to C18 alkylene diisocyanate；

(ii) C3 to C8 aklylene glycol；With

D) by oneself of summation meter 0.4 weight % of weight based on caprolactam and thermoplastic polyurethane to 3.4 weight % The alkali metal salt of lactams or alkali salt are mixed into the liquefied mixture in c) following to obtain as polymerization catalyst Mixture: described mixture comprises described caprolactam and described thermoplastic polyurethane and caprolactam and thermoplastic polyurethane Mass ratio is 3:1 to 1:4, then temperature T of 100 DEG C to 175 DEG C₂Under carry out being polymerized to obtain described thermoplastic copolymer, Polymerization in d) carries out 0.1min to 20min,

Preparation in c) and d) in be mixed into and be polymerized be to carry out with discontinuous method, and wherein according to a) provide oneself Lactams is solid state, and is solid state according to thermoplastic polyurethane b) provided, and in c), will be own interior by mediating Amide mixes with thermoplastic polyurethane and the mixture of acquisition is heated to T₁。

Unexpectedly, the rate of polymerization ratio that the batch mode of operation of the present invention provides is for preparing based on polycaprolactam Higher with the rate of polymerization of the standard copolymerization method of the copolymer of thermoplastic polyurethane, and advantageously, even if at e.g., from about 140 DEG C Oligomerization temperature T₂Under also can realize.Therefore, polymerization procedure d) can implement within the shortest time, facilitates joint especially Can efficient method.

Continuous operation mode

Or, the method for the present invention can be implemented in a continuous process, c) in preparation and d) in be mixed into and be polymerized excellent Choosing to include that the continuation method of expressing technique is carried out, c) in preparation enter in the outside of the extruder for expressing technique OK, by being delivered to the extruder for expressing technique according to mixture c) prepared, then in the inside of extruder is carried out d) Polymerization.Preferably, it is solid state according to caprolactam a) provided, is solid, shaped according to thermoplastic polyurethane b) provided State, and in c), by carrying out in an extruder mediating, caprolactam is mixed with thermoplastic polyurethane and mixed by obtain Compound is heated to T₁.Mixture in preferably making c) is at T₁Lower holding 5min to 3h, more preferably 10min to 2h, more preferably 20min To 1h.

Preferably, polymerization catalyst is added at least one first area of extruder and the mixture in c) is added Entering at least one second area of extruder, at least one second area wherein said is at least one firstth district described The downstream in territory.

Optionally, in d), polymerization activator can be also mixed into.In principle, described polymerization activator can internal at extruder or Outside any correct position mixes.Such as, before or after according to d) polymerization catalyst being mixed into, can be by described poly- Close activator to be mixed into the c of preparation outside extruder) c of preparation in mixture or inside extruder) in mixture.Preferably Ground, by described polymerization activator mixing to the c of preparation outside extruder) in mixture.

A) caprolactam is provided；

(i) C3 to C18 alkylene diisocyanate；

(ii) C3 to C8 aklylene glycol；With

C) temperature T of 100 DEG C to 160 DEG C₁Lower preparation comprises described caprolactam and the liquid of described thermoplastic polyurethane State mixture；

D) by oneself of summation meter 0.4 weight % of weight based on caprolactam and thermoplastic polyurethane to 3.4 weight % Alkali metal salt or the alkali salt of lactams are mixed into liquefied mixture c) as polymerization catalyst, following mixed to obtain Compound: described mixture comprises described caprolactam and the mixture of described thermoplastic polyurethane and caprolactam and thermoplastic poly The mass ratio of urethane is 3:1 to 1:4, then temperature T of 100 DEG C to 175 DEG C₂Under carry out being polymerized obtaining described thermoplasticity altogether Polymers, d) in polymerization carry out 1min to 6min,

Preparation in c) and d) in be mixed into and be polymerized the continuation method being to include expressing technique and carry out, c) In preparation carry out in the outside of the extruder for expressing technique, will be delivered to for extruding work according to mixture c) prepared The extruder of skill, the then polymerization in the inside of extruder is carried out d).

A) caprolactam is provided；

(i) C3 to C18 alkylene diisocyanate；

(ii) C3 to C8 aklylene glycol；With

D) by oneself of summation meter 0.4 weight % of weight based on caprolactam and thermoplastic polyurethane to 3.4 weight % The alkali metal salt of lactams or alkali salt are mixed into the liquefied mixture in c) as polymerization catalyst, following to obtain Mixture: described mixture comprises described caprolactam and the mixture of described thermoplastic polyurethane and caprolactam and thermoplasticity The mass ratio of polyurethane is 3:1 to 1:4, then temperature T of 100 DEG C to 175 DEG C₂Under carry out being polymerized to obtain described thermoplasticity Copolymer, polymerization d) carries out 1min to 6min,

Preparation in c) and d) in be mixed into and be polymerized the continuation method being to include expressing technique and carry out, c) In preparation carry out in the outside of the extruder for expressing technique, will be delivered to for extruding work according to mixture c) prepared The extruder of skill, the then polymerization in the inside of extruder is carried out d),

D) also include summation meter 1 weight % of weight based on caprolactam and thermoplastic polyurethane to 12 weights The polymerization activator of amount % is mixed into the c of preparation outside extruder) in mixture, wherein said polymerization activator is selected from N, N '-C2 to N, N '-C12 alkylenediamino formoxyl caprolactam and the mixture of two or more thereof.

Or, the method for the present invention can be implemented in a continuous process, c) in preparation and d) in be mixed into and be polymerized That the continuation method including expressing technique is carried out, c) in preparation and d) in polymerization be for expressing technique squeeze The inside going out machine is carried out.

Preferably, this selectable continuous operation mode is: provide the caprolactam of liquid condition, b) middle offer in a) The thermoplastic polyurethane of solid state, is then delivered to the thermoplastic polyurethane of the caprolactam of liquid condition with solid state Extruder.

In this selectable continuous operation mode, it is preferable that be not less than T₀At a temperature of, at extruder at least In one first area, described thermoplastic polyurethane is made to be transformed into liquid condition.It is further preferred that at least the one of extruder At least one second area described in individual second area adds in the downstream of at least one first area of extruder Caprolactam, with the mixture in obtaining c).Additionally, it is preferred that described at least one the 3rd region of extruder at least one Individual 3rd region adds polymerization catalyst in the downstream of at least one second area of extruder, and carries out step d) In polymerization.

Optionally, in this selectable continuous operation mode, in d), also can be mixed into polymerization activator, wherein by institute State polymerization activator to add to the second area of extruder with the form with the mixture of caprolactam.

A) caprolactam is provided；

(i) C3 to C18 alkylene diisocyanate；

(ii) C3 to C8 aklylene glycol；With

D) alkali metal salt or the alkali salt of caprolactam are mixed into liquefied mixture c) as polymerization catalyst In, to obtain following mixture: described mixture comprises described caprolactam and described thermoplastic polyurethane and wherein acyl in oneself Amine is 3:1 to 1:4 with the mass ratio of thermoplastic polyurethane, then temperature T of 100 DEG C to 175 DEG C₂Under carry out being polymerized obtaining Described thermoplastic copolymer, d) in polymerization carry out 1min to 6min,

Preparation in c) and d) in be mixed into and be polymerized the continuation method being to include expressing technique and carry out, c) In preparation and d) in the inside being aggregated in the extruder for expressing technique carry out.

Unexpectedly, the rate of polymerization that the continuous operation mode of the present invention provides is higher than for preparing based on polycaprolactam The rate of polymerization of the standard copolymerization method of the copolymer of amine and thermoplastic polyurethane, and advantageously, though oligomeric at about 140 DEG C Close temperature T₂Under also can realize.Therefore, d) in polymerization preferably carry out 0.5min to 10min, more preferably 1min to 6min, more excellent Select 1.5min to 4min.Therefore, polymerization procedure d) can implement within the advantageously short time, facilitates the side of special efficient energy-saving Method.

Preferably, above two continuation method also includes the method step e) according to copolymer pelletize d) obtained.Excellent Selection of land, above two continuation method also includes the method step f) according to copolymer annealing d) obtained, more preferably by basis D) the method step f) that acquisition the copolymer according to e) pelletize are annealed.F) annealing in preferably 60 DEG C to 170 DEG C, more preferably Carry out at a temperature of 90 DEG C to 150 DEG C, more preferably 100 DEG C to 130 DEG C.

Thermoplastic copolymer

I () alkylene diisocyanate, (ii) aklylene glycol are not subject to the alkylene moiety in (iii) polyalkylene ether Any special restriction, and can be the most each substituted or unsubstituted state.Such as, the alkylidene of state it is replaced Part preferably has one or more than one substituent group, more preferably one to three substituent group, more preferably one substituent group.Substituent group Can be similar and different.Such as, substituent group must step c) or d) under conditions of be inertia, here it is preferably moieties Reason.C1-C6 moieties be it is furthermore preferred that and C1-C3 moieties even more preferably from.

(iii) polyalkylene ether in is preferably selected from poly-(C1 to C20 alkylidene) ether and two or more mixture thereof, Further preferably selected from poly-(C2 to C12 alkylidene) ether and two or more mixture thereof, further preferably (C2 is extremely selected from poly- C6 alkylidene) ether and two or more mixture, the wherein polyalkylene ether the most poly-tetrahydrochysene furan in (iii) Mutter.

(i) alkylene diisocyanate, (ii) aklylene glycol and the concrete alkylene base portion in (iii) polyalkylene ether The carbon atom number specified is divided to refer to the total number of the carbon atom in alkylene moiety.Such as, " C20 alkylidene " is interpreted as meaning Refer to the alkylene moiety with 20 carbon atoms.

(iii) the polyalkylene ether preferred number-average molecular weight (M in_n) be 300g to 8000g, more preferably 600g extremely 4500g, more preferably 800g to 2500g.

Preferably, thermoplastic polyurethane is based on following material: according to (i) selected from C1 to C20 alkylene diisocyanate and The alkylene diisocyanate of its two or more mixture；According to (ii) selected from C1 to C20 aklylene glycol and two Kind or the aklylene glycol of more kinds of mixture；With according to (iii) selected from poly-(C1 to C20 alkylidene) ether and two kinds or more Number-average molecular weight (the M of multiple mixture_n) it is the polyalkylene ether of 300g to 8000g.It is highly preferred that thermoplastic polyurethane base In following material: according to (i) selected from C6 to C13 alkylene diisocyanate and the alkylidene of the mixture of two or more thereof Diisocyanate；According to (ii) selected from C4 to C6 aklylene glycol and the aklylene glycol of the mixture of two or more thereof； With the number-average molecular weight (M being selected from poly-(C2 to C6 alkylidene) ether according to (iii)_n) it is the polyalkylene ether of 600g to 4500g.More Preferably, thermoplastic polyurethane is based on following material: according to (i) selected from 1, and 6-hexamethylene diisocyanate (HDI), 4,4 '- Diisocyanate base-dicyclohexyl methyl hydride (H12MDI), 1-NCO-3-isocyanatomethyl-3,5,5-trimethyl Hexamethylene (IPDI) and the alkylene diisocyanate of the mixture of two or more thereof；According to (ii) selected from 1,4-butanediol With 1,6-HD and the aklylene glycol of mixture thereof；It is selected from number-average molecular weight (M with according to (iii)_n) be 800g to 2500g The polyalkylene ether of PolyTHF.It is highly preferred that the thermoplastic polyurethane in b) is based on following material: (i) 1,6-six Methylene diisocyanate (HDI) or 4,4 '-diisocyanate base dicyclohexyl methyl hydride (H12MDI)；(ii) 1,4-butanediol or 1,6-HD；(iii) number-average molecular weight (M_n) it is the PolyTHF of 800g to 2500g.

Preferably, in component alkylene diisocyanate (i), aklylene glycol (ii) and polyalkylene ether (iii) Kind or more kinds of, preferably two or more, the most all there is straight chain and/or cyclic alkylidene part, more preferably described Alkylene diisocyanate (i) has straight chain and/or cyclic alkylidene part, and described aklylene glycol (ii) has straight chain alkylene Base section and described polyalkylene ether (iii) have straight-chain alkyl-sub-part.

The term " straight chain and/or cyclic alkylidene part " used in this specification is understood to mean that by least one straight The alkylene moiety that chain alkylene moiety and at least one cyclic alkylidene part are combined into, such as 4,4 '-diisocyanate base The dicyclohexyl methyl hydride part of dicyclohexyl methyl hydride (H12MDI).

Described thermoplastic polyurethane preferably has 10 000g to 300 000g, more preferably 15 000g to 200 000g, more Number-average molecular weight (the M of preferably 19 000g to 160 000g_n)。

In the thermoplastic copolymer of the present invention, the content of the lactams of non-copolymerization is preferably not greater than 10 weight %, more preferably It is not more than 7 weight %, more preferably no more than 5 weight %, weight based on thermoplastic copolymer and the lactams of non-copolymerization total And meter.

The amount of the thermoplastic polyurethane that the thermoplastic copolymer of the present invention preferably comprises is 30 to 75 weight %, is more preferably 33 weight % to 70 weight %, more preferably 36 weight % to 64 weight %, based on the own interior acyl being present in described copolymer The summation meter of the weight of amine and thermoplastic polyurethane.

Preferably such a is based on polycaprolactam and the thermoplastic copolymer of thermoplastic polyurethane, described thermoplasticity Polyurethane-base in:

(i) C3 to C18 alkylene diisocyanate；

(ii) C3 to C8 aklylene glycol；With

Wherein said copolymer comprises the thermoplastic polyurethane of 25 weight % to 80 weight %, based on being present in described copolymerization Caprolactam in thing and the summation meter of the weight of thermoplastic polyurethane.

Preferably, the elastic modelling quantity of the thermoplastic copolymer of the present invention is up to 1500MPa, and more preferably 100MPa is extremely 1500MPa, more preferably 300MPa to 700MPa, measure according to DIN EN ISO 527.

Preferably, the fracture strength of the thermoplastic copolymer of the present invention is up to 80MPa, more preferably 5MPa to 80MPa, More preferably 10MPa to 30MPa, measures according to DIN EN ISO 527.

Preferably, the maximum fracture strength of the thermoplastic copolymer of the present invention is up to 90MPa, and more preferably 5MPa is extremely 90MPa, more preferably 10MPa to 30MPa, measure according to DIN EN ISO 527.

Preferably, the elongation at break of the thermoplastic copolymer of the present invention is 200% to 800%, more preferably 300% to 700%, more preferably 400% to 600%, measure according to DIN EN ISO 527.

Preferably, the thermoplastic copolymer of the present invention by the present invention provide for preparation based on polycaprolactam and heat The method of the thermoplastic copolymer of plastic polyurethane and obtain maybe can by the present invention provide for preparation based on polycaprolactam The method of the thermoplastic copolymer of amine and thermoplastic polyurethane obtains.It is highly preferred that the thermoplastic copolymer of the present invention is to pass through The method of the present invention obtains maybe can be provided by the form of the pellet that the method for the present invention obtains.It is highly preferred that the heat of the present invention Plastic copolymer maybe can be carried by the form of the pellet of the annealing that the method for the present invention obtains to be obtained by the method for the present invention Supply.

Moulded products

In principle, moulded products special is not limited by any.Such as, described moulded products can be solid shaped articles, That is: there is no goods in chamber, or have the hollw article in chamber, such as flexible pipe.Described moulded products is preferably hollw article, more preferably Flexible pipe, more preferably pneumatic hose.

Preferably, the burst strength of described moulded products is 30bar to 60bar, more preferably 35bar to 55bar, more excellent Elect 40bar to 50bar as.Thus, the moulded products of the present invention is particularly suitable for those flexible pipes that must endure as high pressure, example Such as pneumatic hose.

Preferably, described moulded products includes at least one filler.In principle, described filler is not by any special limit System.Described filler can include organic material or inorganic material, be selected from glass, silicate, carbon black, graphite, metal-oxide, Metal carbonate, metal sulfate and the inorganic material of the mixture of two or more thereof, or such as aromatic polyamides polymerization The organic material of thing.Such as, filler can mix or in order to strengthen described moulded products as pigment, antistatic additive, fire retardant Mechanical performance and mix.The form of filler special is not limited by any.Filler can be particle form (such as, powdery, granular Or spherical), or be fiber or the form of braided fiber (woven fiber).Preferably, described filler includes glass fibre, more Preferably braided glass fibre.In above-mentioned discontinuous method, preferably during the polymerization in d), it is mixed into described fiber, Qi Zhongju Close and carry out in a mold, preferably carry out in reaction injection molding (RIM) mould.

Moulded products is preferably made up of thermoplastic copolymer based on polycaprolactam and thermoplastic polyurethane, described thermoplastic Property polyurethane-base in

(i) C3 to C18 alkylene diisocyanate；

(ii) C3 to C8 aklylene glycol；With

Purposes

The method that the present invention also provides for utilizing the thermoplastic copolymer of the present invention to manufacture moulded products.Described moulded products is excellent Elect hollw article as, preferably flexible pipe, more preferably pneumatic hose.Preferably, described moulded products comprises at least one filler, more excellent Select glass filler, more preferably braided glass fibre.

By following preferred embodiment and by membership relation and other combinations thereof quoted and obtain to the present invention Carry out the brightest:

1. prepare based on polycaprolactam and a method for the thermoplastic copolymer of thermoplastic polyurethane, comprising:

A) caprolactam is provided；

(i) alkylene diisocyanate；

(ii) aklylene glycol；With

(iii) polyalkylene ether；

C) in temperature T₁Lower preparation comprises described caprolactam and the liquefied mixture of described thermoplastic polyurethane；

D) polymerization catalyst is mixed into the liquefied mixture in c) to obtain following mixture: described mixture comprises Described caprolactam is 3:1 to 1:4 with the mass ratio of described thermoplastic polyurethane and caprolactam and thermoplastic polyurethane, then Temperature T of up to 175 DEG C₂Lower polymerization is to obtain described thermoplastic copolymer.

2. according to the method described in embodiment 1, wherein pass through a) provide solid state or molten condition, more preferably The caprolactam of molten condition.

3. according to the method described in embodiment 1 or 2, i) in alkylene diisocyanate sub-selected from C1 to C20 Alkylene diisocyanate and the mixture of two or more thereof, be preferably selected from C3 to C18 alkylene diisocyanate and two Kind or more kinds of mixture, be more preferably selected from C6 to C13 alkylene diisocyanate and the mixture of two or more thereof, Be more preferably selected from 1,6-hexamethylene diisocyanate (HDI), 4,4'-diisocyanate base dicyclohexyl methyl hydride (H12MDI), 1-NCO-3-isocyanatomethyl-3,5,5-trimethyl-cyclohexane (IPDI) and the mixing of two or more thereof Thing.

4., according to the method according to any one of embodiment 1-3, wherein the aklylene glycol in (ii) is selected from C1 to C20 Aklylene glycol and the mixture of two or more thereof, be preferably selected from C3 to C8 aklylene glycol and two or more Mixture, is more preferably selected from C4 to C6 aklylene glycol and the mixture of two or more thereof, is more preferably selected from Isosorbide-5-Nitrae-fourth two Alcohol, 1,6-HD and mixture thereof.

5., according to the method according to any one of embodiment 1-4, wherein the polyalkylene ether in (iii) is selected from poly-(C1 To C20 alkylidene) ether and two or more multiple mixture thereof, it is preferably selected from poly-(C2 to C12 alkylidene) ether and two kinds Or more kinds of mixture, it is more preferably selected from poly-(C2 to C6 alkylidene) ether and the mixture of two or more thereof, wherein (iii) polyalkylene ether in is more preferably PolyTHF.

6. according to the method according to any one of embodiment 1-5, wherein component alkylene diisocyanate (i), alkylene In base glycol (ii) and polyalkylene ether (iii) one or more of, preferably two or more, the most all have straight Chain and/or cyclic alkylidene part, wherein it is highly preferred that described alkylene diisocyanate (i) has straight chain and/or ring-type Asia Moieties, described aklylene glycol (ii) has straight-chain alkyl-sub-part and described polyalkylene ether (iii) has straight chain Asia Moieties.

7. according to the method according to any one of embodiment 1-6, the wherein equal molecule of number of the polyalkylene ether in (iii) Amount (M_n) be 300g to 8000g, be preferably 600g to 4500g, be more preferably 800g to 2500g.

8. according to the method according to any one of embodiment 1-7, b) in the equal molecule of number of thermoplastic polyurethane Amount (M_n) be 10 000g to 300 000g, be preferably 15 000g to 200 000g, be more preferably 19 000g to 160 000g.

9. according to the method according to any one of embodiment 1-8, wherein T₀Being 155 DEG C to 280 DEG C, preferably 160 DEG C extremely 250 DEG C, more preferably 170 DEG C to 230 DEG C.

10. according to the method according to any one of embodiment 1-9, wherein T₁It is not more than T₀, wherein T₁It is preferably 100 DEG C To 175 DEG C, more preferably 100 DEG C to 160 DEG C, more preferably 110 DEG C to 150 DEG C.

11. according to the method according to any one of embodiment 1-10, wherein T₂It is 100 DEG C to 175 DEG C, preferably 115 DEG C To 170 DEG C, more preferably 130 DEG C to 170 DEG C.

12. according to the method according to any one of embodiment 1-11, wherein T₂Not less than T₁, meanwhile, temperature difference T₂-T₁Excellent Elect 0 DEG C to 40 DEG C as, more preferably 0 DEG C to 30 DEG C, more preferably 0 DEG C to 20 DEG C.

13. according to the method according to any one of embodiment 1-12, d) in polymerization catalyst be caprolactam Salt, the preferably alkali metal salt of caprolactam or the alkali metal salt of alkali salt, more preferably caprolactam, more preferably acyl in oneself The sodium salt of the sodium salt of amine or potassium salt, more preferably caprolactam

14. according to the method according to any one of embodiment 1-13, the amount of the polymerization catalyst being wherein mixed in d) It is 0.2 weight % to 4 weight %, is preferably 0.4 weight % to 3.4 weight %, is more preferably 0.6 weight % to 3 weight %, base In caprolactam and the summation meter of the weight of thermoplastic polyurethane.

15. according to the method according to any one of embodiment 1-14, is wherein additionally mixed into polymerization activation in step d) Agent.

16. according to the method described in embodiment 15, wherein said polymerization activator selected from the substituted lactams of N-carbonyl, Aliphatic series and aromatic diisocyanates, allophanate, polyisocyanates, aliphatic series and aromatics diacyl halogen and two or more Mixture, be preferably selected from N, N '-C1-to N, N '-C20-alkylenediamino formoxyl caprolactam, N, N '-alkylidene two Carbamoyl caprolactam, N-acetyl group C3-C10 lactams, C2-C16 alkylene diisocyanate, C5-C12 arlydene two Isocyanates, C5-C16 arylidene alkylene diisocyanate, C1-C6 alkylidene allophanate, C12-C24 alkylidene polyisocyanate Cyanate, C2-C16 alkylidene diacyl halogen, C5-C12 arlydene diacyl halogen or C5-C16 arylidene alkylene diacyl halogen And the mixture of two or more, it is more preferably selected from the own interior acyl of N, N '-C3-to N, N '-C8-alkylenediamino formoxyl Amine, N-acetyl group C4-C8 lactams, C4-C13 alkylene diisocyanate, C6-C10 arylene diisocyanate, C7-C10 are sub- Aryl alkene group diisocyanate, C2-C4 alkylidene allophanate, C16-C20 alkylidene polyisocyanates, C4-C13 alkylene Base diacyl halogen, C6-C10 arlydene diacyl halogen or C8-C12 arylidene alkylene diacyl halogen and two or more Mixture.

17. according to the method described in embodiment 15 or 16, wherein said polymerization activator selected from N, N '-hexa-methylene- 1,6-dicarbamoyl base caprolactam, vinylcaprolactam, tetramethylene diisocyanate, hexamethylene diisocyanate, Di-2-ethylhexylphosphine oxide (cyclohexyl isocyanate)；Toluene di-isocyanate(TDI), ethyl allophanate, 1,6-hexamethylene diisocyanate (HDI) trimer, butylidene diacyl bromine, hexa-methylene diacyl chlorine, 4,4 '-di-2-ethylhexylphosphine oxide (cyclohexyl acid chloride), first Phenylmethylene diacyl chlorine and the mixture of two or more thereof.

18. are selected from N, N '-Asia according to the method according to any one of embodiment 15-17, wherein said polymerization activator Alkyl dicarbamoyl base caprolactam and the mixture of two or more thereof, be preferably selected from N, N '-C1 to N, N '-C20 sub- Alkyl dicarbamoyl base caprolactam and the mixture of two or more thereof, be more preferably selected from N, N '-C2 to N, N '-C12 Alkylenediamino formoxyl caprolactam and the mixture of two or more thereof, be more preferably selected from N, N '-C3 to N, N '-C8 Alkylenediamino formoxyl caprolactam and the mixture of two or more thereof, wherein, it is highly preferred that described polymerization activation Agent is N, N '-hexa-methylene-1,6-dicarbamoyl base caprolactam.

19. according to the method according to any one of embodiment 15-18, and the amount of the polymerization activator being wherein mixed into is 0.5 Weight % is to 15 weight %, preferably 1 weight % to 12 weight %, more preferably 2 weight % to 9 weight %, based on acyl in oneself The summation meter of the weight of amine and thermoplastic polyurethane.

20. according to the method according to any one of embodiment 1-19, wherein according in thermoplastic copolymer d) obtained The content of lactams of non-copolymerization be not more than 10 weight %, preferably no greater than 7 weight %, more preferably no more than 5 weight %, base In thermoplastic copolymer and the summation meter of the weight of the lactams of non-copolymerization.

21. according to the method according to any one of embodiment 1-20, wherein according to d) being mixed into polymerization catalyst to c) In liquefied mixture in obtain following mixture: described mixture comprise described caprolactam and described thermoplastic polyurethane and Caprolactam and the mass ratio of thermoplastic polyurethane are 7:3 to 1:3, preferred 2:1 to 3:7, more preferably 16:9 to 9:16.

22. according to the method according to any one of embodiment 1-21, wherein according to preparation c) with according to being mixed into d) And polymerization with discontinuous method or is carried out in a continuous process, carry out the most in a continuous process, more preferably to include the company of expressing technique Continuous method is carried out.

23. are carried out with discontinuous method according to the method described in embodiment 22, wherein said method, wherein according to a) providing Caprolactam be molten condition, be solid state according to thermoplastic polyurethane b) provided, and c) in liquefied mixture lead to Crossing to be mixed into described thermoplastic polyurethane provides to the caprolactam of molten condition.

24. according to the method described in embodiment 23, wherein by the mixture in c) in temperature T₁Lower holding 1min is extremely 1.5h, more preferably 10min to 70min, more preferably 20min to 60min.

25. according to the method described in embodiment 23 or 24, wherein in step d), interior to comprise polymerization catalyst and oneself Described polymerization catalyst is mixed into by the form of the liquefied mixture of amide.

26. according to the method described in embodiment 25, and the wherein said liquid comprising polymerization catalyst and caprolactam is mixed Compound is to provide to the caprolactam of molten condition by being mixed into by described polymerization catalyst.

27. according to the method described in embodiment 25 or 26, the wherein said liquid comprising polymerization catalyst and caprolactam The amount of the polymerization catalyst that state mixture contains be 0.4 weight % to 8 weight %, be preferably 0.8 weight % to 6.8 weight %, More preferably 1.2 weight % to 6 weight %, weight meter based on described caprolactam.

28. according to the method according to any one of embodiment 25-27, wherein will comprise polymerization catalyst and caprolactam Liquefied mixture in temperature T₃Lower holding 1min to 1.5h, preferred 10min to 70min, more preferably 20min to 60min.

29. according to the method described in embodiment 28, wherein T₃Being 100 DEG C to 175 DEG C, more preferably 105 DEG C to 155 DEG C, more preferably 110 DEG C to 130 DEG C.

30. according to the method according to any one of embodiment 23-29, is wherein mixed into polymerization activation in d) further Agent, and the most described polymerization activator is mixed into the mixture in c).

31. according to the method described in embodiment 30, the amount of the polymerization activator being wherein mixed in the mixture in c) It is 1 weight % to 30 weight %, is preferably 2 weight % to 24 weight %, is more preferably 4 weight % to 18 weight %, based on oneself The summation meter of the weight of lactams and thermoplastic polyurethane.

32. according to the method according to any one of embodiment 25-31, wherein in d), will comprise polymerization catalyst and The liquefied mixture of caprolactam is mixed into the liquefied mixture in c), and comprises the mixing of polymerization catalyst and caprolactam The mass ratio of thing and mixture c) is 1:4 to 3:1, preferred 1:3 to 2:1, more preferably 1:1.5 to 1.5:1.

33. according to the method according to any one of embodiment 25-32, wherein in temperature T₄Lower will comprise polymerization catalyst With the liquefied mixture of caprolactam with c) in liquefied mixture mix.

34. according to the method according to any one of embodiment 25-33, wherein temperature T₄Be 100 DEG C to 175 DEG C, preferably It it is 105 DEG C to 155 DEG C, more preferably 110 DEG C to 130 DEG C.

35. according to the method according to any one of embodiment 23-34, d) in polymerization carry out 0.1min extremely 20min, preferred 0.3min to 10min, more preferably 0.5min to 3min.

36. are carried out with discontinuous method according to the method described in embodiment 22, wherein said method, wherein according to a) providing Caprolactam be solid state, be solid state according to thermoplastic polyurethane b) provided, and make oneself by kneading in c) Lactams mixes with thermoplastic polyurethane and the mixture of acquisition is heated to T₁。

37. according to the method described in embodiment 36, wherein by the mixture in c) at T₁Lower holding 0.1min is extremely 20min, preferred 0.3min to 16min, more preferably 0.5min to 12min.

38. according to the method described in embodiment 36 or 37, d) in polymerization carry out 0.1min to 20min, preferably 0.3min to 10min, more preferably 0.5min to 3min.

39. according to the method described in embodiment 22, c) in preparation and d) in be mixed into and be polymerized be to include The continuation method of expressing technique is carried out, c) in preparation carry out in the outside of the extruder for expressing technique, by basis C) mixture prepared is delivered to the extruder for expressing technique, then gathering in the inside of described extruder is carried out d) Close.

40. according to the method described in embodiment 39, is wherein solid state according to caprolactam a) provided, according to b) The thermoplastic polyurethane provided is solid state, and in c), makes caprolactam and heat by carrying out in an extruder mediating The mixture of acquisition is also heated to T by plastic polyurethane mixing₁。

41. according to the method described in embodiment 39 or 40, and the mixture in wherein making c) is at T₁Lower holding 5min to 3h, Preferably 10min to 2h, more preferably 20min to 1h.

42. according to the method according to any one of embodiment 39-41, wherein adds described polymerization catalyst to extrusion In at least one first area of machine, and the mixture in c) is added at least one second area of extruder, wherein At least one second area described is the downstream at least one first area described.

43. according to the method according to any one of embodiment 39-42, wherein further mixed polymerization activation in d) Agent, and described polymerization activator is mixed into the c of preparation outside extruder) in mixture.

44. according to the method according to any one of embodiment 39-43, d) in be aggregated at least the one of extruder Individual region carries out 0.5min to 10min, preferred 1min to 6min, more preferably 1.5min to 4min.

45. according to the method described in embodiment 22, c) in preparation and d) in be mixed into and be polymerized be to include The continuation method of expressing technique is carried out, c) in preparation and d) in polymerization be in the extruder of expressing technique Portion is carried out.

46. according to the method described in embodiment 45, a) the middle caprolactam providing liquid condition, and b) middle offer The thermoplastic polyurethane of solid state, is then delivered to the caprolactam of liquid condition and the thermoplastic polyurethane of solid state Extruder.

47. according to the method described in embodiment 45 or 46, is wherein being not less than T₀At a temperature of at extruder at least In one first area, described thermoplastic polyurethane is made to be transformed into liquid condition.

48. according to the method described in embodiment 47, wherein described at least one second area of extruder extremely A few second area is to add caprolactam in the downstream of at least one first area of extruder with in acquisition c) Mixture.

49. according to the method described in embodiment 48, wherein described at least one the 3rd region of extruder extremely Few 3rd region is to add described polyalcohol catalyst also in the downstream of at least one second area of extruder Carry out step d) polymerization.

50. according to the method according to any one of embodiment 45-49, is wherein mixed into polymerization activation in d) further Agent, and described polymerization activator is to be injected towards in the second area of extruder with the form of the mixture with caprolactam.

51. according to the method according to any one of embodiment 45-50, d) in polymerization carry out 0.5min extremely 10min, preferred 1min to 6min, more preferably 1.5min to 4min.

52. according to the method according to any one of embodiment 1-51, and it also includes:

E) will be according to copolymer pelletize d) obtained.

53. according to the method according to any one of embodiment 1-52, and it also includes:

F) preferably to 150 DEG C, more preferably 100 DEG C to 130 DEG C, root is made 60 DEG C to 170 DEG C, more preferably 90 DEG C According to copolymer d) obtained, preferably according to d) obtaining and annealing according to the copolymer of e) pelletize.

54. according to the method according to any one of embodiment 23-35, d) in polymerization carry out in a mold, excellent It is selected in reaction injection molding (RIM) mould and carries out.

55. 1 kinds based on polycaprolactam and the thermoplastic copolymer of thermoplastic polyurethane, described thermoplastic polyurethane base In

(i) alkylene diisocyanate；

(ii) aklylene glycol；With

(iii) polyalkylene ether,

56. according to the thermoplastic copolymer described in embodiment 55, and wherein the alkylene diisocyanate in (i) is selected from C1 To C20 alkylene diisocyanate and the mixture of two or more thereof, it is preferably selected from C3 to C18 alkylene diisocyanate And the mixture of two or more, be more preferably selected from C6 to C13 alkylene diisocyanate and two or more Mixture, is more preferably selected from 1,6-hexamethylene diisocyanate (HDI), 4,4 '-diisocyanate base dicyclohexyl methyl hydride (H12MDI), 1-NCO-3-isocyanatomethyl-3,5,5-trimethyl-cyclohexane (IPDI) and two or more The mixture planted.

57. according to the thermoplastic copolymer described in embodiment 55 or 56, and wherein the aklylene glycol in (ii) is selected from C1 To C20 aklylene glycol and the mixture of two or more thereof, it is preferably selected from C3 to C8 aklylene glycol and two kinds or more Multiple mixture, is more preferably selected from C4 to C6 aklylene glycol and the mixture of two or more thereof, is more preferably selected from 1, 4-butanediol, 1,6-HD and mixture thereof.

58. according to the thermoplastic copolymer according to any one of embodiment 55-57, the wherein polyalkylene in (iii) Ether is selected from poly-(C1 to C20 alkylidene) ether and the mixture of two or more thereof, is preferably selected from poly-(C2 to C12 alkylidene) ether And the mixture of two or more, further preferably selected from poly-(C2 to C6 alkylidene) ether and two or more is mixed Compound, wherein the polyalkylene ether more preferably PolyTHF in (iii).

59. according to the thermoplastic copolymer according to any one of embodiment 55-58, wherein component alkylidene two Carbimide. Ester (i), aklylene glycol (ii) and polyalkylene ether (iii) one or more of, preferably two or more, the most complete Portion has straight chain and/or a cyclic alkylidene part, wherein it is highly preferred that described alkylene diisocyanate (i) have straight chain and/ Or cyclic alkylidene part, described aklylene glycol (ii) has straight-chain alkyl-sub-part and described polyalkylene ether (iii) tool There is straight-chain alkyl-sub-part.

60. according to the thermoplastic copolymer according to any one of embodiment 55-59, the interior acyl of its non-copolymerization being had The content of amine is not more than 10 weight %, preferably no greater than 7 weight %, and more preferably no more than 5 weight %, based on thermoplastic copolymer The summation meter of the weight of the lactams of non-copolymerization.

61. according to the thermoplastic copolymer according to any one of embodiment 55-60, the wherein polyalkylene in (iii) Number-average molecular weight (the M of ether_n) be 300g to 8000g, preferred 600g to 4500g, more preferably 800g to 2500g.

62. according to the thermoplastic copolymer according to any one of embodiment 55-61, wherein said thermoplastic polyurethane Number-average molecular weight (M_n) be 10 000g to 300 000g, preferably 15 000g to 200 000g, more preferably 19 000g to 160 000g。

63. according to the thermoplastic copolymer according to any one of embodiment 55-62, the heat that wherein said copolymer comprises The amount of plastic polyurethane is that 30 weight % to 75 weight %, preferably 33 weight % to 70 weight %, more preferably 36 weight % are to 64 Weight %, based on the caprolactam being present in described copolymer and the summation meter of the weight of thermoplastic polyurethane.

64. are up to 1500MPa according to the thermoplastic copolymer described in embodiment 63, its elastic modelling quantity, are preferably 100MPa to 1500MPa, more preferably 300MPa to 700MPa, measure according to DIN EN ISO 527.

65. according to the thermoplastic copolymer described in embodiment 63 or 64, and its fracture strength is up to 80MPa, is preferably 5MPa to 80MPa, more preferably 10MPa to 30MPa, measure according to DIN EN ISO 527.

66. according to the thermoplastic copolymer according to any one of embodiment 63-65, and its maximum fracture strength is up to 90MPa, preferably 5MPa to 90MPa, preferably 10MPa to 30MPa, measure according to DIN EN ISO 527.

67. according to the thermoplastic copolymer according to any one of embodiment 63-66, its elongation at break be 200% to 800%, preferably 300% to 700%, more preferably 400% to 600%, measure according to DIN EN ISO 527.

68. according to the thermoplastic copolymer according to any one of embodiment 55-67, and it is by appointing in embodiment 1-54 One described method is obtained and maybe can be obtained by the method according to any one of embodiment 1-54, preferably by embodiment party Method any one of case 52 and 53 obtains the shape of the pellet that maybe can be obtained by the method any one of embodiment 52 and 53 Formula, more preferably obtains the shape of the annealing pellet that maybe can be obtained by the method for embodiment 53 by the method for embodiment 53 Formula.

69. 1 kinds by any one of embodiment 55-68 thermoplastic copolymer obtain or can be by embodiment 55-68 The moulded products that the thermoplastic copolymer of any one obtains.

70. according to the moulded products described in embodiment 69, and wherein said moulded products is hollw article, the softest Pipe, more preferably pneumatic hose.

71. according to the moulded products described in embodiment 69 or 70, and its burst strength is 30bar to 60bar, is preferably 35bar to 55bar, more preferably 40bar to 50bar.

72. comprise at least one according to the moulded products according to any one of embodiment 69-71, wherein said moulded products Kind of filler, described filler is preferably according to the d described in embodiment 54) in polymerization process in be injected towards in mould.

73. include glass fibre according to the moulded products described in embodiment 72, wherein said filler, preferably weave glass Fiber.

74. use the method that the thermoplastic copolymer any one of embodiment 55-68 manufactures moulded products.

75. according to the method described in embodiment 74, and wherein said moulded products is hollw article, preferably flexible pipe, more It is preferably pneumatic hose.

76. comprise at least one filler, preferably glass according to the method described in embodiment 74, wherein said moulded products Fiber, more preferably braided glass fibre.

In the examples below the present invention is carried out more specific elaboration.

Embodiment

The raw material that use is presented herein below in EXPERIMENTAL EXAMPLE and comparative example, as follows:

1. lactams:

Caprolactam, purchased from BASF.

2. thermoplastic polyurethane (TPU), available from BASF:

Elastollan A1185A is (own based on PolyTHF 1000, hexamethylene diisocyanate (HDI) and 1,6- The TPU of glycol), anneal at 110 DEG C 3h；

Elastollan L1185A is (based on PolyTHF, 4,4 '-diisocyanate base dicyclohexyl methyl hydride (H12MDI) and the TPU of BDO), at 110 DEG C anneal 3h；

Elastollan E1170A is (based on PolyTHF 1000/2000, methylenediphenyl diisocyanates (MDI) TPU with BDO), anneal at 110 DEG C 3h.

3. polymerization catalyst:

Br ü ggolen C10 (17%-19% sodium caprolactam in caprolactam), purchased from Br ü ggemann KG, Heilbronn。

4. polymerization activator:

Br ü ggolen C20 (80% hexa-methylene-1 in caprolactam, 6-dicarbamoyl base caprolactam), purchases From Br ü ggemann KG, Heilbronn.

Embodiment 1A

Polyreaction is carried out under dry nitrogen atmosphere in the round-bottomed flask of 250mL.By caprolactam at 170 DEG C (120g) fusing, is then mixed into the thermoplastic polyurethane (40 weight %) (Elastollan A1185A) of 80g.By this mixture At T₁30min is stirred at=170 DEG C.Then, the catalyst (Br ü ggolen C10) of 23.1g (11.6 weight %) is introduced to In fused solution mixture, thus start polyreaction.This anionic polymerisation is at T₂Carry out at=170 DEG C, and logical after 1min Cross and make reactor cool down in frozen water (0 DEG C) and stop.

Embodiment 1B

Elastollan L1185A thermoplastic polyurethane is used to replace Elastollan A1185A to repeat embodiment 1A.

Embodiment 1C

Repeating embodiment 1A and 1B, difference is: by thermoplastic polyurethane at a temperature of 140 DEG C rather than 170 DEG C Dissolve, the mixture of caprolactam and thermoplastic polyurethane will be comprised at T₁=140 DEG C rather than T₁30min is stirred at=170 DEG C, And polyreaction is at T₂=140 DEG C rather than T₂Carry out at=170 DEG C.

Embodiment 2A

The reative cell of the 60mL of flow graph (Haake Polylab OS) is polymerized.Described reative cell is heated to 170 DEG C, and it is simultaneously charged into the caprolactam (60 weight %) of 35g and the thermoplastic polyurethane (40 weight %) of 23.3g (Elastollan A1185A).By described component at T₁Mix 10min at=170 DEG C, be then mixed into the catalyst (Br of 6.71g ü ggolenC10) to start anionic polymerisation, and make described anionic polymerisation at T₂Carry out at=170 DEG C.By reactant mixture Mediate 15min again.

Embodiment 2B

Elastollan L1185A thermoplastic polyurethane is used to replace Elastollan A1185A to repeat embodiment 2A.

Embodiment 2C

Repeating embodiment 2A and 2B, difference is: by thermoplastic polyurethane at T₁=140 DEG C rather than T₁=170 DEG C At a temperature of mix, and polyreaction is at T₂=140 DEG C rather than T₂Carry out at a temperature of=170 DEG C.

Embodiment 3

Thermoplastic copolymer based on polycaprolactam and thermoplastic polyurethane is at double screw extruder (ZSK 32, L/D= 56, Werner&Pfleiderer) upper preparation, described double screw extruder connects heatable blending tank at region 2.Use nitrogen Gas purges extruder and blending tank continuously.In blending tank by heating and stir 2 hours and prepare 60 weight % oneself in acyl The uniform liquefied mixture of the thermoplastic polyurethane (Elastollan A1185A) of amine and 40 weight %.By this mixture Temperature regulates at T₁=140 DEG C.Copolymer is by following preparation: by solid metric method urging 11.6 weight % at 60 DEG C Agent (Br ü ggolen C10) is mixed into the region 1 of extruder, and at T₂By caprolactam-polyurethane mixing at=170 DEG C Thing liquid meter is in region 2.At T₂Realize being polymerized with the rotating speed of 200rpm at=170 DEG C in the 3-15 of region.To be formed Copolymer by separating and pelletize under water, then at 80 DEG C anneal.Total residence time in an extruder is about 3min.

Embodiment 4

Repeating embodiment 3, difference is: by caprolactam-polyurethane mixture premixing 30min rather than 2h, and At T₁=140 DEG C rather than T₁Measure at=170 DEG C to the region 2 of extruder, and be aggregated in T₂=140 DEG C rather than T₂=170 Carry out in the 3-12 of region at DEG C.Additionally, the temperature in region 13,14 and 15 is respectively set as 150 DEG C, 160 DEG C and 170 DEG C.

Embodiment 5

Repeating embodiment 3, difference is: by caprolactam-polyurethane mixture premixing 30min rather than 2h.This Outward, catalyst concn is reduced to 5 weight %.

Comparing embodiment

Repeating embodiment 3, difference is: use Elastollan E1170A thermoplastic polyurethane to replace Elastollan A1185A, and make caprolactam-polyurethane mixture at T₁=180 DEG C rather than T₁Mix at=140 DEG C, and Measured to region 2 at 180 DEG C rather than 170 DEG C.Additionally, the temperature in the 13-15 of region is set as T₂=180 DEG C rather than T₂=170 DEG C.

Embodiment 6

Repeating embodiment 3, difference is: use the caprolactam of 40 weight % and the thermoplastic poly ammonia of 60 weight % Ester rather than the caprolactam of 60 weight % and the thermoplastic polyurethane of 40 weight %, and by caprolactam and thermoplastic polyurethane Premixing 30min rather than 2 hours.

Embodiment 7

Repeating embodiment 3, difference is: add 5.1 in the caprolactam-polyurethane mixture in mixing container The activator (Br ü ggolen C20) of weight %.

Embodiment 8

Thermoplastic copolymer based on polycaprolactam and thermoplastic polyurethane squeezes at the twin screw purged continuously with nitrogen Go out and carry out on machine (ZSK 32, L/D=56, Werner&Pfleiderer).Copolymer preparation is as follows: by the thermoplastic of 40 weight % Property the metering of polyurethane (Elastollan A1185A) solid in region 1 (120 DEG C), and make it in region 2 (160 DEG C), region Fusing in 3 (220 DEG C) and region 4 (180 DEG C), subsequently by the caprolactam liquid meter of 60 weight % to region 5 (140 DEG C) In.Subsequent sections is heated to 170 DEG C, then by the catalyst of 11.6 weight % (Br ü ggolen C10) is passed through solid Metering is mixed into and starts polymerization to region 7.Total residence time in an extruder is about 3min.The copolymer formed is led to Cross and separate and pelletize annealing at 80 DEG C under water.

Embodiment 9

Repeating embodiment 8, difference is: use the caprolactam of 40 weight % and the thermoplastic poly ammonia of 60 weight % Ester (A1185A), rather than the caprolactam of 60 weight % and the thermoplastic polyurethane of 40 weight %.

The mensuration of burst strength

Measuring the burst strength of the moulded products of hose form, the external diameter of described flexible pipe is 8.2mm and wall thickness is 8.2mm. For this purpose it is proposed, sealed one end of the tubing sample of 30cm length, and the other end is made to be connected to compressed air confession by controlling valve To device.The pressure in tubing sample is made to be gradually increasing (with the speed of about 30bar/15s) until 23 DEG C or the temperature control of 70 DEG C Room occurs explosion.It is burst pressure by pressure record during explosion, because the expansion before flexible pipe explosion can be deduced by it.Each Test is in triplicate.

Table 1

Embodiments of the invention clearly show and use the method for the present invention to create beat all effect.As implemented Shown in example 1-9 (it is made according to the present invention), due to according to specific TPU copolymer b) provided, method step d) In polymerization can be at the favourable low temperature T of not higher than 175 DEG C₂Under carry out.By contrast, as shown in comparing embodiment, it is provided that The polymerization temperature that the step of TPU copolymer based on aromatic diisocyanates (such as MDI) needs is about 180 DEG C.

Quote document

-G.S.Yang et al., " Preparation and characterisation of thermoplastic polyurethane elastomer and polyamide 6 blends by in situ anionic ring-opening Polymerization of epsilon-caprolactam ", Polymer Engineering and Science 2006, 46, the 1196-1203 page

-G.S.Yang et al., " A novel approach to the preparation of thermoplastic polyurethane elastomer and polyamide 6 blends by in situ anionic ring-opening Polymerisation of ε-caprolactam ", Polym.Int.2006,55, the 643-649 page

-DE 10 2006 036 539 A1

Claims

A) caprolactam is provided；

(i) alkylene diisocyanate；

(ii) aklylene glycol；With

(iii) polyalkylene ether；

D) polymerization catalyst is mixed into the liquefied mixture in c) to obtain following mixture: described mixture comprises described Caprolactam and described thermoplastic polyurethane and caprolactam are 3:1 to 1:4 with the mass ratio of thermoplastic polyurethane, then Temperature T of up to 175 DEG C₂Under carry out being polymerized to obtain described thermoplastic copolymer.

Method the most according to claim 1, wherein the alkylene diisocyanate in (i) is selected from C1 to C20 alkylidene two Isocyanates and the mixture of two or more thereof, be preferably selected from C3 to C18 alkylene diisocyanate and two kinds or more Multiple mixture, is more preferably selected from C6 to C13 alkylene diisocyanate and the mixture of two or more thereof, more preferably Selected from 1,6-hexamethylene diisocyanate (HDI), 4,4'-diisocyanate base dicyclohexyl methyl hydride (H12MDI), 1-isocyanide Perester radical-3-isocyanatomethyl-3,5,5-trimethyl-cyclohexane (IPDI) and the mixture of two or more thereof.

Method the most according to claim 1 and 2, wherein the aklylene glycol in (ii) is selected from C1 to C20 aklylene glycol And the mixture of two or more, it is preferably selected from C3 to C8 aklylene glycol and the mixture of two or more thereof, more Be preferably selected from C4 to C6 aklylene glycol and the mixture of two or more thereof, be more preferably selected from BDO, 1,6-oneself Glycol and mixture thereof.

4., according to the method according to any one of claim 1-3, wherein the polyalkylene ether in (iii) is selected from poly-(C1 to C20 Alkylidene) ether and the mixture of two or more thereof, be preferably selected from poly-(C2 to C12 alkylidene) ether and two or more Mixture, further preferably selected from poly-(C2 to C6 alkylidene) ether and the mixture of two or more thereof, wherein in (iii) Polyalkylene ether more preferably PolyTHF.

5. according to the method according to any one of claim 1-4, wherein component alkylene diisocyanate (i), alkylidene two In alcohol (ii) and polyalkylene ether (iii) one or more of, preferably two or more, the most all there is straight chain And/or cyclic alkylidene part, wherein it is highly preferred that described alkylene diisocyanate (i) has straight chain and/or ring-type alkylene Base section, described aklylene glycol (ii) has straight-chain alkyl-sub-part and described polyalkylene ether (iii) has straight chain alkylene Base section.

6. according to the method according to any one of claim 1-5, wherein T₀Being 155 DEG C to 280 DEG C, preferably 160 DEG C to 250 DEG C, more preferably 170 DEG C to 230 DEG C.

7. according to the method according to any one of claim 1-6, wherein T₁It is not more than T₀, wherein T₁It is preferably 100 DEG C to 175 DEG C, more preferably 100 DEG C to 160 DEG C, more preferably 110 DEG C to 150 DEG C.

8. according to the method according to any one of claim 1-7, wherein T₂Being 100 DEG C to 175 DEG C, preferably 115 DEG C to 170 DEG C, more preferably 130 DEG C to 170 DEG C.

9. according to the method according to any one of claim 1-8, d) in the salt that polymerization catalyst is caprolactam, excellent Elect alkali metal salt or the alkali salt of caprolactam, the more preferably alkali metal salt of caprolactam as, more preferably acyl in oneself The sodium salt of the sodium salt of amine or potassium salt, more preferably caprolactam.

10., according to the method according to any one of claim 1-9, d) also include mixed polymerization activator, wherein said Polymerization activator is preferably selected from N-carbonyl-substituted lactams, aliphatic series and aromatic diisocyanates, allophanate, many isocyanides Acid esters, aliphatic series and aromatics diacyl halogen and the mixture of two or more thereof, be preferably selected from N, N '-C1 to N, N '-C20-sub- Acyl in alkyl dicarbamoyl base caprolactam, N, N '-alkylenediamino formoxyl caprolactam, N-acetyl group C3-C10 Amine, C2-C16 alkylene diisocyanate, C5-C12 arylene diisocyanate or C5-C16 arylidene alkylene two Carbimide. Ester, C1-C6 alkylidene allophanate, C12-C24 alkylidene polyisocyanates, C2-C16 alkylidene diacyl halogen, C5-C12 Arlydene diacyl halogen or C5-C16 arylidene alkylene diacyl halogen and the mixture of two or more thereof, be more preferably selected from N, N '-C3-to N, N '-C8-alkylenediamino formoxyl caprolactam, N-acetyl group C4-C8 lactams, C4-C13 alkylidene Diisocyanate, C6-C10 arylene diisocyanate or C7-C10 arylidene alkylene diisocyanate, C2-C4 alkylidene urea Carbamate, C16-C20 alkylidene polyisocyanates, C4-C13 alkylidene diacyl halogen, C6-C10 arlydene diacyl halogen or C8-C12 arylidene alkylene diacyl halogen and the mixture of two or more thereof.

11. according to the method according to any one of claim 1-10, wherein according to d) by polymerization catalyst mixing in c) Liquefied mixture provides following mixture: described mixture comprises described caprolactam and described thermoplastic polyurethane and oneself is interior Amide and the mass ratio of thermoplastic polyurethane are 7:3 to 1:3, preferred 2:1 to 3:7, more preferably 16:9 to 9:16.

12. according to the method according to any one of claim 1-11, wherein according to preparation c) with according to being mixed into and poly-d) Conjunction is with discontinuous method or to carry out in a continuous process, carries out the most in a continuous process, more preferably to include the continuous of expressing technique Method is carried out.

13. 1 kinds based on polycaprolactam and the thermoplastic copolymer of thermoplastic polyurethane, described thermoplastic polyurethane based on

(i) alkylene diisocyanate；

(ii) aklylene glycol；With

(iii) polyalkylene ether,

The amount of the thermoplastic polyurethane that wherein said copolymer comprises is 25 weight % to 80 weight %, described common based on being present in Caprolactam in polymers and the summation meter of the weight of thermoplastic polyurethane.

14. thermoplastic copolymers according to claim 13, wherein the alkylene diisocyanate in (i) is selected from C1 extremely C20 alkylene diisocyanate and the mixture of two or more thereof, be preferably selected from C3 to C18 alkylene diisocyanate and Its two or more mixture, is more preferably selected from C6 to C13 alkylene diisocyanate and two or more is mixed Compound, is more preferably selected from 1,6-hexamethylene diisocyanate (HDI), 4,4 '-diisocyanate base dicyclohexyl methyl hydride (H12MDI), 1-NCO-3-isocyanatomethyl-3,5,5-trimethyl-cyclohexane (IPDI) and two or more The mixture planted.

15. according to the thermoplastic copolymer described in claim 13 or 14, and wherein the aklylene glycol in (ii) is selected from C1 to C20 Aklylene glycol and the mixture of two or more thereof, be preferably selected from C3 to C8 aklylene glycol and two or more Mixture, is more preferably selected from C4 to C6 aklylene glycol and the mixture of two or more thereof, is more preferably selected from Isosorbide-5-Nitrae-fourth two Alcohol, 1,6-HD and mixture thereof.

16. according to the thermoplastic copolymer according to any one of claim 13-15, and wherein the polyalkylene ether in (iii) is Selected from poly-(C1 to C20 alkylidene) ether and the mixture of two or more thereof, be preferably selected from poly-(C2 to C12 alkylidene) ether and Its two or more mixture, further preferably selected from poly-(C2 to C6 alkylidene) ether and the mixing of two or more thereof Thing, wherein the polyalkylene ether more preferably PolyTHF in (iii).

17. according to the thermoplastic copolymer according to any one of claim 13-16, wherein component alkylene diisocyanate (i), aklylene glycol (ii) and polyalkylene ether (iii) one or more of, preferably two or more, whole There is straight chain and/or cyclic alkylidene part, wherein it is highly preferred that described alkylene diisocyanate (i) have straight chain and/or Cyclic alkylidene part, described aklylene glycol (ii) has straight-chain alkyl-sub-part and described polyalkylene ether (iii) has Straight-chain alkyl-sub-part.

18. according to the thermoplastic copolymer according to any one of claim 13-17, the thermoplasticity that wherein said copolymer comprises The amount of polyurethane be 30 weight % to 75 weight %, preferably 33 weight % are to 70 weight %, and more preferably 36 weight % are to 64 Weight %, based on the caprolactam being present in described copolymer and the summation meter of the weight of thermoplastic polyurethane.

19. according to the thermoplastic copolymer according to any one of claim 13-18, and it is by appointing according in claim 1-12 One described method obtains maybe can be passed through to obtain according to the method according to any one of claim 1-12.

20. moulded products, it is made up of the thermoplastic copolymer any one of claim 13-19 or can be by claim 13- Thermoplastic copolymer any one of 19 obtains.

21. use the method manufacturing moulded products according to the thermoplastic copolymer according to any one of claim 13-19.